Phthalocyanine azo dyes containing 5-cyano-dichloropyrimidyl group

ABSTRACT

Compounds of the formulae ##STR1## salts thereof, and mixtures of such compounds or salts, 
     wherein Me, Pc, Q 1 , R 1 , R 2 , R 3 , Y, a, b, c and d as defined, 
     useful as fiber-reactive dyes for dyeing or printing hydroxy group- and nitrogen-containing organic substrates, for example, textile material comprising cotton, the obtained dyeings and prints having good all-round fastnesses, such as good light fastness.

This is a continuation-in-part of application Ser. No. 07/411,945, filed Sep. 25, 1989 and now abandoned.

The invention relates to phthalocyanine compounds which contain a heterocyclic fibre-reactive group, a process for their production and their use as fibre-reactive dyes in dyeing and printing processes.

More particularly, this invention provides comparison of formula Ia ##STR2## in free acid or salt form and mixtures thereof, in which Pc is the phthalocyanine radical,

Me is Cu, Ni, Co, Fe or Al,

a is 1, 2 or 3, and

b is 0, 1 or 2, provided that the sum of a and b is a maximum of 3;

each R₂ and R₃ is independently hydrogen or C₁₋₆ alkyl, or --NR₂ R₃ is a five- or six-membered cyclic ring system or a five- or six-membered cyclic ring system which contains one further oxygen or nitrogen atom,

each R₁ is independently hydrogen, unsubstituted C₁₋₄ alkyl or C₁₋₄ alkyl monosubstituted by hydroxy, halogen, --SO₃ H, --OSO₃ H or --COOH,

Z is ##STR3## Q₂ is ##STR4## in which the * denotes the carbon atom attached to --SO₂ NR₁ --,

R₄ is hydrogen, halogen, hydroxy, C₁₋₄ alkyl, C₁₋₄ alkoxy, --COOH or --SO₃ H; and

Y is ##STR5## is which the * indicates the coupling position to which --N═N-- is attached,

R₅ is C₁₋₄ alkyl or --COR₈,

R₈ is --OH, --OC₁₋₄ alkyl or --NH₂,

Q₃ is a divalent bridging group,

R₉ is hydrogen, C₁₋₄ alkyl, C₅₋₆ cycloalkyl, phenyl or phenyl-(C₁₋₄ alkyl) in which each phenyl ring is unsubstituted or substituted by one to three substituents selected from C₁₋₄ alkyl, C₁₋₄ alkoxy, halogen, --COOH and --SO₃ H, --COR₈, --(CH₂)_(n) --SO₃ H, --(CH₂)_(n) --OSO₃ H or --(CH₂)_(n) --COR₈ in which R₈ is as defined above and n is 1, 2, 3 or 4,

R₁₀ is hydrogen, --CN, --SO₃ H, --COR₈, C₁₋₄ alkyl, C₁₋₄ alkyl monosubstituted by --OH, halogen, --CN, C₁₋₄ alkoxy, ##STR6## --SO₃ H, --OSO₃ H or --NH₂, --SO₂ NH₂, ##STR7## wherein R₈ is as defined above, each R₇ is hydrogen, halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, --COOH or --SO₃ H,

R₁₁ is hydrogen, C₁₋₄ alkyl or C₂₋₄ hydroxyalkyl, and

An⊖ is a non-chromophoric anion; and

Q₄ is C₂₋₆ alkylene, monohydroxy-substituted C₃₋₆ alkylene or C₂₋₆ alkylene which is interrupted by one radical selected from --O-- and --NR₁ --, ##STR8## in which the C₁₋₄ alkylene radicals and the free valences in the second and third structural formulae are most preferably para to each other, or

--Q₄ --NR₁ -- is ##STR9## in which m is 0 to 1, and the * denotes the carbon atoms attached to the nitrogen atom of the pyridone ring.

Furthermore, this invention provides compounds of formula Ib ##STR10## in free acid or salt form and mixtures thereof, in which c is 1 or 2, and

d is 1 or 2,

provided that the sum of c and d is a maximum of 3;

R is C₁₋₆ -alkyl and

R₃ is hydrogen or C₁₋₆ alkyl or

--NRR₃ is a five- or six-membered cyclic ring system or a five- or six-membered cyclic ring system which contains one further oxygen or nitrogen atom,

Q₁ is C₂₋₆ alkylene, monohydroxy-substituted C₃₋₆ alkylene or C₂₋₆ alkylene which is interrupted by one radical selected from --O-- and --NR₁ --, ##STR11## in which the * denotes the carbon atom attached to --SO₂ NR₁ --, or

--SO₂ NR₁ --Q₁ --NR₁ -- is ##STR12## and Pc, Me, R₁, R₄ and Z are as defined above.

In the specification, any alkyl or alkylene group capable of being linear or branched is linear or branched unless indicated to the contrary. In a hydroxy-substituted alkyl or alkylene group which is bonded to nitrogen, the hydroxy group is preferably attached to a carbon atom which is not directly bonded to nitrogen.

Preferably, the total number of anionic groups and, more preferably, the number of sulpho groups exceeds the number of cationic groups, if any, by at least one.

Preferably, none of the four units of the phthalocyanine ring system contains more than one substituent.

Halogen is fluorine, chlorine or bromine, preferably chlorine or bromine and especially chlorine.

Due to the non-selectivity of the reaction of 5-cyano-2,4,6-trichloropyrimidine with the --NHR₁ group of the chromophore which occurs by displacement of either of the chloro atoms in the 2- and 6-positions of the pyrimidine ring, the position in which Z is attached is not fixed.

Preferably the compounds of formulae Ia and Ib are isomeric mixtures in which the positions of the substituents on the phthalocyanine radical and the position in which Z is attached are not fixed.

Preferably, Me is Me₁, where Me₁ is copper or nickel.

Preferably, R₁ is hydrogen, C₁₋₂ alkyl or by hydroxy, --SO₃ H, --OSO₃ H or --COOH, of which hydroxy is most preferred.

Preferably, each R₁ is R_(1a), where each R_(1a) is independently hydrogen, methyl, ethyl, 2-hydroxyethyl, --(CH₂)_(p) SO₃ H, --(CH₂)_(p) OSO₃ H or --(CH₂)_(q) COOH, in which p is 1 or 2 and q is 1, 2 or 3. More preferably each R₁ is R_(1b), where each R_(1b) is independently hydrogen, methyl, ethyl or 2-hydroxyethyl and most preferably each R₁ is R_(1c), where each R_(1c) is independently hydrogen or methyl.

Preferably, each R₂ and R₃ is R_(2a) and R_(3a), where each R_(2a) and R_(3a) is independently hydrogen or C₁₋₄ alkyl, or R_(2a) and R_(3a), together with the nitrogen atom to which they are attached, form a pyrrolidine, piperidine, morpholine or piperazine ring. More preferably each R₂ and R₃ is R_(2b) and R_(3b), where each R_(2b) and R_(3b) is independently hydrogen, methyl or ethyl.

Preferably R is R_(a), where R_(a) is C₁₋₄ alkyl; more preferably R is R_(b), where R_(b) is methyl or ethyl; or --NR_(a) R_(3a) is a pyrrolidine, piperidine, morpholine or piperazine ring.

Any R₄ is preferably R_(4a), where R_(4a) is hydrogen, methyl, methoxy, --COOH or --SO₃ H. More preferably, R₄ is R_(4b) is hydrogen, --COOH or --SO₃ H.

Preferably, Q₁ is Q_(1a), where Q_(1a) is --C₂₋₃ alkylene, monohydroxysubstituted --C₃₋₄ alkylene-, --C₂₋₃ alkylene--O--C₂₋₃ alkylene-, --C₂₋₃ -alkylene-NR_(1b) --C₂₋₃ alkylene-, ##STR13## --NR₁ --Q_(1a) --NR₁ -- is ##STR14## in which the * denotes the carbon atoms attached to --SO₂ NR₁ --.

More preferably Q₁ is Q_(1b), where Q_(1b) is --C₂₋₃ alkylene-, monohydroxy-substituted --C₃₋₄ alkylene-, ##STR15## or --SO₂ --NR₁ --Q_(1b) --NR₁ -- is ##STR16##

Even more preferably Q₁ is Q_(1c), where Q_(1c) is --C₂₋₃ alkylene-, monohydroxy-substituted ##STR17## or --SO₂ NR₁ --Q_(1c) --NR₁ -- is ##STR18## most preferably Q₁ is Q_(1d), where Q_(1d) is --C₂₋₃ alkylene- or monohydroxy-substituted --C₃₋₄ alkylene-.

Preferably R₅ --OH.

Preferably R₆ is R_(6a), where R_(6a) is methyl, --COOH or --CONH₂.

Preferably R₇ is R_(7a), where R_(7a) is hydrogen, chlorine, methyl, methoxy, --COOH or --SO₃ H.

Preferably R₈ is R_(8a), where R_(8a) is --OH or --NH₂.

Preferably Q₃ is Q_(3a), where Q_(3a) is ##STR19##

More preferably Q₃ is Q_(3b), where Q_(3b) is ##STR20##

Preferably R₉ is R_(9a), where R_(9a) is hydrogen, methyl, ethyl, phenyl, --COR_(8a), --CH₂ SO₃ H or --CH₂ OSO₃ H. More preferably R₉ is R_(9b), where R_(9b) is methyl or ethyl, most preferably methyl.

Preferably R₁₀ is R_(10a), where R_(10a) is hydrogen, --CN, --SO₃ H, --COR_(8a) or --CH₂ SO₃ H. More preferably R₁₀ is R_(10b), where R_(10b) is hydrogen or --CONH₂.

Preferably Q₄ is Q_(4a), where Q_(4a) is --C₂₋₄ alkylene-, monohydroxy-substituted --C₃₋₄ alkylene-, ##STR21## --Q_(4a) --NR₁ -- is in which the * denotes the carbon atoms attached to the nitrogen atom of the pyridone ring.

Y is preferably Y_(a), more preferably Y_(b), where Y_(a) and Y_(b) are as defined below.

Preferably Q₂ is Q_(2a), where Q_(2a) is ##STR22## in which Y_(a) is ##STR23##

More preferably Q₂ is Q_(2b), where Q_(2b) is ##STR24## in which Y_(b) is ##STR25## in which R_(9b) is most preferably methyl.

In any significance of Q₁, Q_(1a) -Q_(1c), Q₂, Q_(2a), Q_(2b), Q₃, Q_(3a), Q_(3b), Q₄ and Q_(4a) having a phenylene or substituted phenylene radical, unless otherwise indicated, the free valences (or the free valence and the radical containing the free valence) are preferably meta or para to each other.

Preferred compounds of formula Ia are those of formula Ia' and mixtures thereof ##STR26## which compounds or mixtures are in free acid or salt form, in which the symbols are as defined above; and

a₁ is 2 or 3, and

b₁ is 0 or 1, provided that the sum of a₁ and b₁ is a maximum of 3.

More preferred compounds of formula Ia' are those in which

a₁ is 2 or 3 and b₁ is zero;

R_(9b) in Q_(2b) is methyl; and

R_(1b) is hydrogen or methyl.

Preferred compounds of formula Ib are those of formula Ib' and mixtures thereof ##STR27## which compounds or mixtures are in free acid or salt form, in which the symbols are as defined above.

More preferred compounds of formula Ib' are those in which

d is 1;

R_(a) is R_(b) and R_(3a) is R_(3b) ;

R_(1b) is hydrogen or methyl; and

Q_(1b) is q_(1c) and most preferably Q_(1d).

Even more preferred compounds of formula Ib' are those wherein Q_(1b) is Q_(1d), and Me₁ is Cu.

When a compound of formula Ia or Ib is in salt form, the cation associated with the sulpho groups and any carboxy group is not critical and may be any one of those non-chromophoric cations conventional in the field of fibre-reactive dyes provided that the corresponding salts are water-soluble.

Examples of suitable cations are alkali metal ions and unsubstituted and substituted ammonium ions, for example lithium, sodium, potassium, ammonium, mono-, di-, tri- and tetra-methylammonium, triethylammonium and mono-, di- and tri-ethanolammonium.

Preferably the cations are selected from the alkali metal ions and ammonium, more preferably sodium.

In a compound of formula Ia or Ib the cations of the sulpho and any carboxy groups can be the same or different, e.g., they can also be a mixture of the above mentioned cations meaning that the compound of formula Ia or Ib can be in a mixed salt form.

The invention further provides a process for preparing a compound of formula Ia or Ib or a mixture of compounds of formula Ia or Ib, which comprises reacting a compound of formula IIa or IIb, ##STR28## in which the symbols are as defined above, or a mixture of compounds of formula IIa or IIb with 5-cyano-2,4,6-trichloropyrimidine, in appropriate molar amounts, i.e., the molar ratio of the latter to the former is usually 1-1.3:1.

The reaction is suitably carried out at 0° to 40° C. and at pH 6.5 to 9. Water is normally used as the reaction medium, but an organic solvent such as acetone can be used as solvent for the 5-cyano-2,4,6-trichloropyrimidine.

The compounds of formulae Ia and Ib may be isolated in accordance with known methods, for example by conventional salting out with alkali metal salt, filtering and drying in vacuo at a slightly elevated temperature.

Depending on the reaction and isolation conditions, a compound of formula Ia or Ib is obtained in free acid or preferably salt form or even mixed salt form containing, for example, one or more of the above-mentioned cations. It may be converted from free acid form to a salt form or mixture of salt forms or vice versa of from one salt form to another by conventional means.

The starting compounds of formulae IIa and IIb are either known or may be prepared in accordance with known methods from known starting compounds.

The compounds of formulae Ia and Ib and mixtures of compounds of formula Ia or Ib are fibre-reactive dyes. They are suitable for dyeing or printing hydroxy group- or nitrogen-containing organic substrates. They can for example be used for dyeing or printing leather and fibres, filaments or textiles produced therefrom which comprise natural or synthetic polyamides or natural or regenerated cellulose material, e.g., cotton, viscose or rayon staple fibre, and preferably textile materials comprising cotton.

Methods for dyeing include dyebaths or printing pastes commonly used with fibre-reactive dyes. For example, cotton is preferably dyed by the exhaust process, for example from a long or short bath and at a temperature from 30° to 80° C.

Preferred compounds according to the invention are those which have good cold dyeing properties and may be used for cold-dyeing at temperatures of about 60°C.

The compounds according to the invention may be used per se or in combination with appropriate fibre-reactive dyes of the same class which possess comparable dyeing properties, e.g., all-round fastness properties, extent of ability to exhaust from the dyebath onto the fibre, etc. The combination dyeings obtained have fastness properties which are as good as that of dyeings made with an individual dye.

Good exhaust and fixation values are obtained with the compounds of formulae Ia and Ib. The unfixed part of the dye can be easily washed out. The dyeings and prints obtained have good light fastness. In addition, they have good washing fastness and wet fastness properties, for example to water, sea water and sweat, and have good resistance to oxidation caused by for example chlorine-containing water, hypochlorite bleaches, peroxide bleaches and perborate-containing detergents.

The following examples further serve to illustrate the invention. All parts and percentages are by weight and all temperatures are given in degrees centigrade unless indicated to the contrary.

In the examples, each symbol Z used in the formulae means a group ##STR29##

EXAMPLE 1

29.8 Parts of a copper phthalocyanine dyestuff base compound containing per molecule on average 2 sulphonic acid groups, 1 N,N-dimethylsulphamide group and 1 substituted phenylsulphamide group, produced by sulphochlorinating copper phthalocyanine and subsequently reacting with dimethylamine and 1,3-diaminobenzene, are dissolved in 200 parts of water at pH 6.5 to 7.0. 150 Parts of ice are added and a solution of 6.3 parts of 5-cyano-2,4,6-trichloropyrimidine in acetone (20% excess) is added as a single addition. The pH of the reaction mixture drops and is held at pH 7 to 7.5 for the duration of the reaction by the continuous addition of 20% soda solution. At the same time the reaction temperature is raised to and maintained at 20°. After 3 to 4 hours, the reaction is complete. The mixture is salted out with 45 parts of sodium chloride, and the dyestuff deposit obtained is filtered off under suction and dried at 35°. The dyestuff obtained is of formula 1a ##STR30## and dyes cellulose material, especially cotton, a brilliant turquoise shade. The dyeings have good light fastness and wet fastness properties.

EXAMPLE 2

By using, instead of the 29.8 parts of the copper phthalocyanine dyestuff base compound of Example 1, an equivalent amount of a nickel phthalocyanine dyestuff base compound having an average 2 sulphonic acid groups, 1 N,N-dimethylsulphamide group and 1 substituted phenylsulphamide group per molecule of dyestuff base compound (i.e. 29.6 parts), the nickel analogue of the dyestuff of formula 1a is obtained, which dyes cotton a blue-green shade and produces dyeings with good fastness properties.

EXAMPLES 3-10

Using a method analogous to that described in Examples 1 and 2, and starting with the appropriate starting compounds, the following compounds of formula IA (represented in free acid form) ##STR31## may be prepared in which the symbols are as defined in Table 1 below. The table gives the shade of dyeing on cotton for each example, in which

bt is brilliant turquoise and

bg is bluish green.

These cotton dyeings have good fastness properties.

                  TABLE 1                                                          ______________________________________                                         Compounds of formula IA                                                                                          position                                                               R.sub.4 (position                                                                      of --NH--                                                                              shade on                             Ex. No.                                                                               Me     R      R.sub.3                                                                             in ring)                                                                               in ring cotton                               ______________________________________                                         3      Cu     CH.sub.3                                                                              H    H       3       bt                                   4      Cu     C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                     H       3       bt                                   5      Cu     C.sub.2 H.sub.5                                                                       H    4-SO.sub.3 H                                                                           3       bt                                   6      Cu     CH.sub.3                                                                              H    2-COOH  4       bt                                   7      Cu     C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                     H       4       bt                                   8      Ni     CH.sub.3                                                                              H    H       3       bg                                   9      Ni     C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                     H       4       bg                                   10     Ni     C.sub.2 H.sub.5                                                                       H    3-SO.sub.3 H                                                                           4       bg                                   ______________________________________                                    

EXAMPLE 11

25.5 Parts of a nickel phthalocyanine dyestuff base compound containing on average 2.5 sulphonic acid groups and 1 substituted phenylsulphamide group per molecule, produced by sulphochlorinating nickel phthalocyanine and subsequently reacting with 1,3-diaminobenzene-4-sulphonic acid, are mixed by stirring with 1.8 parts of sodium nitrite in 150 parts of water. The solution is cooled to 0°-2° and is added drop-wise to a solution of 12 parts of 30% hydrochloric acid in 100 parts of ice/water. The diazonium salt suspension obtained is maintained at a temperature of 0°-5° and is passed into a solution consisting of 300 parts of ice/water and 5.9 parts of 1-(3-methylaminopropyl)-6-hydroxy-4-methyl-2-pyridone. During the coupling reaction, the pH is maintained at 9-9.5 by adding 20% sodium hydroxide solution. Following the method of Example 1, the resulting green solution is reacted with 5-cyano-2,4,6-trichloropyrimidine and the product is isolated. The dyestuff of formula 11 a. ##STR32## is obtained. It dyes cellulose material, especially cotton, a brilliant green shade. These dyeings have good light fastness and excellent wet fastness properties.

EXAMPLES 12-50

Using a method analogous to that of Example 11 and using appropriate starting materials the following compounds of formulae IB and IC (represented in free acid form) ##STR33## may be prepared in which the symbols are as defined in Tables 2 and 3 below. The dyestuffs of Examples 12-50 give green dyeings on cotton which have high fixation yields and good fastnesses, such as good light and wet fastness properties. Compounds in which Me is nickel give particularly brilliant dyeings on cotton.

                                      TABLE 2                                      __________________________________________________________________________     Compounds of formula IB                                                        Ex. No.                                                                              Me  R.sub.4                                                                             R.sub.10   Q.sub.4NR.sub.1                                      __________________________________________________________________________     12    Cu  H    H                                                                                          ##STR34##                                           13    Cu  SO.sub.3 H                                                                          H          "                                                    14    Cu  "    CONH.sub.2 "                                                    15    Cu  H    CN         "                                                    16    Ni  H    H          "                                                    17    Ni  H                                                                                    ##STR35## "                                                    18    Ni  H    CONH.sub.2 "                                                    19    Ni  SO.sub.3 H                                                                          "          "                                                    20    Ni  H    CN         "                                                    21    Ni  SO.sub.3 H                                                                          CONH.sub.2 (CH.sub.2).sub.2 NH                                  22    Ni  "    H          "                                                    23    Cu  "    H          "                                                    24    Ni  H    H          "                                                    25    Cu  H    H          "                                                    26    Ni  H    H                                                                                          ##STR36##                                           27    Ni  SO.sub. 3 H                                                                         H          "                                                    28    Ni  "    CONH.sub.2 "                                                    29    Ni  "    "          (CH.sub.2).sub.3 NH                                  30    Cu  H    "          "                                                    31    Ni  SO.sub.3 H                                                                          H          "                                                    32    Ni  "    H                                                                                          ##STR37##                                           __________________________________________________________________________

                  TABLE 3                                                          ______________________________________                                         Compounds of formula IC                                                                                          R.sub.7 (in                                                                           position                              Ex. No.                                                                               Me     R.sub.4 R.sub.5                                                                             R.sub.6                                                                               position)                                                                             of --NH--                             ______________________________________                                         33     Cu     SO.sub.3 H                                                                             OH   CH.sub.3                                                                              H      3                                     34     Cu     H       OH   "      2-SO.sub.3 H                                                                          5                                     35     Cu     SO.sub.3 H                                                                             OH   "      "      5                                     36     Cu     "       OH   --COOH H      3                                     37     Cu     "       NH.sub.2                                                                            CH.sub.3                                                                              H      3                                     38     Ni     "       OH   "      H      3                                     39     Ni     H       OH   "      2-SO.sub.3 H                                                                          5                                     40     Ni     SO.sub.3 H                                                                             OH   "      "      5                                     41     Ni     "       OH   --COOH H      4                                     42     Ni     "       NH.sub.2                                                                            CH.sub.3                                                                              H      3                                     43     Ni     "       "    "      2-SO.sub.3 H                                                                          5                                     44     Ni     "       "    "      H      4                                     45     Ni     "       OH   --COOH H      3                                     46     Ni     "       OH   CH.sub.3                                                                              2-SO.sub.3 H                                                                          4                                     47     Ni     "       OH   "      H      4                                     48     Ni     H       OH   --COOH H      3                                     49     Cu     H       OH   CH.sub.3                                                                              H      4                                     50     Ni     H       OH   "      H      3                                     ______________________________________                                    

EXAMPLES 51-58

Using a method analogous to that of Examples 1 to 2 and using appropriate starting materials, the following compounds of formula ID ##STR38## may be prepared in which the symbols are as defined in Table 4 below.

The shade of dyeing on cotton is given in the last column of Table 4 wherein

bt is brilliant turquoise and

bg in bluish green.

These dyeings have good fastness properties.

                  TABLE 4                                                          ______________________________________                                         Compounds of formula ID                                                        Ex. No.                                                                               Me      Q.sub.1NR.sub.1  shade on cotton                                ______________________________________                                         51     Cu      CH.sub.2 CH.sub.2 NH                                                                            bt                                             52     Ni      "                bg                                             53     Cu                                                                                      ##STR39##       bt                                             54     Ni      "                bg                                             55     Cu                                                                                      ##STR40##       bt                                             56     Ni      "                bg                                             57     Cu                                                                                      ##STR41##       bt                                             58     Ni      "                bg                                             ______________________________________                                    

EXAMPLE 59

Using a method analogous to that described in Example 11 and using appropriate starting compounds, the dyestuff of formula 59a ##STR42## is prepared and isolated. Using this dyestuff, brilliant green cotton dyeings are obtained, which have good light and wet fastness properties.

The dyes of Examples 1 to 59 which are prepared in accordance with the method described above are obtained as sodium salts. They may, depending on the reaction/isolation conditions or by reacting the sodium salts in accordance with known methods, also be obtained in free acid form or in other salt forms, for example those salt forms containing one or more cations indicated in the description above.

The dyes of Examples 1 to 59 (and the corresponding free acids and other salt forms) are isomeric mixtures of

a) the compound in which in the group Z ##STR43## the floating chlorine substituent is located in the 2-position of the pyrimidine ring and the corresponding compound in which the chlorine substituent is located in the 6-position; and

b) of the positional isomers which differ with respect to the position of all substituents of the phthalocyanine radical.

Each of the dyes of Examples 1-10 and 51-58 is a mixture of compounds that differ with respect to the values of c and d, the sum of c and d not exceeding 3. In the predominant components of the mixtures, c is 2 and d is 1, but the mixtures also contain as minor components compounds wherein c is other than 2 and d is other than 1, resulting in the average value of c of each mixture being about 2 and the average value of d of each mixture being about 1.

Each of the dyes of Examples 11-50 and 59 is a mixture of compounds that differ with respect to the value of a, the value of a not exceeding 3. In the predominant components of the mixtures a is 2 or 3, but the mixtures also contain as minor components compounds wherein a is other than 2 or 3, resulting in the average value of a of each mixture being between 2 and 3, inclusive, preferably about 2.5.

In general, it is preferred to use the mixtures of the dyestuffs of Examples 1 to 59, as such. Thus a separation into individual isomers is not necessary but if desired can be effected by conventional means.

In the following examples the application of the compounds according to the invention is illustrated.

APPLICATION EXAMPLE A

10 Parts of bleached cotton fabric are added to a dyebath which contains 0.3 part of the dyestuff of formula 1a (Example 1) and 15 parts of Glauber's salt (calcined) in 300 parts of demineralised water. The dyebath is maintained at a temperature of 40° for 30 minutes and subsequently during the addition at intervals of 10 minutes of a total of 6 parts of soda (calcined) in portions of 0.2, 0.6, 1.2 and 4 parts. Dyeing is continued at 40° for one hour. The dyed material is rinsed for 3 minutes under cold running water and for 3 minutes under hot running water and is then washed for 15 minutes in 500 parts of boiling demineralised water in the presence of 0.25 part of Marseille soap. The dyeing is again rinsed for 3 minutes under hot running water, spun and dried in a drying chamber at 70°. A brilliant turquoise cotton dyeing is obtained with good fastnesses. It has especially good light and wet fastness properties and is stable towards oxidation.

APPLICATION EXAMPLE B

10 Parts of bleached cotton material are added to a dyebath containing 10 parts of Glauber's salt (calcined) in 300 parts of demineralised water. The bath is heated to 40° over the course of 10 minutes, then 0.5 part of the dyestuff of formula 1a (Example 1)is added. After a further 30 minutes at 40°, 3 parts of soda (calcined) are added and dyeing is subsequently continued for 45 minute at 40°. The dyed material is rinsed, washed and dried according to the procedure given in Application Example A. A brilliant turquoise cotton dyeing is obtained, with similar to those of properties the dyeing obtained in Application Example A.

APPLICATION EXAMPLE C

Using the method of Application Example A, a cotton fabric is dyed in a dyebath of 0.3 part of the dyestuff of formula 11a (Example 11) with the addition of only 2 parts of soda (calcined) in one portion. The initial temperature of 40° is then increased to 60° and dyeing is continued for one hour at 60°. The dyed material is rinsed, washed and dried according to the procedure given in Application Example A. A brilliant green cotton dyeing with good build-up and especially good light fastness is obtained.

APPLICATION EXAMPLE D

2.5 Parts of the dyestuff of Example 5 are dissolved in 2000 parts of water. 100 parts of cotton fabric are added to the dyebath, and the temperature is maintained at 80° over a period of 10 minutes. 100 Parts of Glauber's salt (calcined) are added to the dyebath followed by the addition 30 minutes later of 20 parts of soda (calcined). Dyeing is continued for one hour at 80°. The dyed material is rinsed, washed and dried according to the procedure given in Application Example A. A brilliant turquoise dyeing with good fastness properties is obtained.

APPLICATION EXAMPLE E

A printing paste consisting of

    ______________________________________                                          40 parts of the dyestuff of formula 1a or 11a                                  100 parts of urea                                                              350 parts of water                                                             500 parts of a 4% sodium alginate thickener                                    10 parts of sodium bicarbonate                                                1000 parts in all                                                              ______________________________________                                    

is applied to cotton material using a known printing process.

The printed material is then steamed for 4-8 minutes at 102°-104° and rinsed for 3 minutes under cold running water, then 3 minutes under hot running water. The fixed cotton material is subsequently washed and dried according to the procedure given in Application Example A. The brilliant turquoise (brilliant green) print has good all-round fastness properties.

Similarly, the dyestuffs of Examples 2 to 10 and 12 to 59 or a mixture of Examples 1 to 59 may be employed to dye or print cotton in accordance with the method given in Application Examples A to E. All dyeings and prints obtained show good fastness properties.

The dyeings and prints obtained with different dyestuffs are of the respective shades indicated in Examples 1 to 59. 

What is claimed is:
 1. A compound of the formula ##STR44## or a salt thereof, or a mixture of such compounds or salts,whereinMe is Cu, Ni, Co, Fe or Al, Pc is the phthalocyanine ring, each R₂ and R₃ is independently hydrogen or C₁₋₆ alkyl, or --NR₂ R₃ is a pyrrolidine, piperidine, piperazine or morpholine ring, R₄ is hydrogen, halo, hydroxy, C₁₋₄ alkyl, C₁₋₄ alkoxy, --COOH or --SO₃ H, Y is ##STR45## wherein Q_(3a) is ##STR46## Q₄ is linear or branched C₂₋₆ alkylene; linear or branched C₃₋₆ alkylene monosubstituted by hydroxy; linear or branched C₂₋₆ alkylene interrupted by one radical selected from --O-- and --NR₁ --; ##STR47## wherein W_(a) is linear or branched C₁₋₄ alkylene,m is 0 or 1, and the * denotes the carbon atom attached to the nitrogen atom of the pyridone ring, or --Q₄ --NR₁ -- is ##STR48## wherein W_(b) is linear or branched C₂₋₄ -alkylene, andthe * denotes the carbon atom attached to the nitrogen atom of the pyridone ring, R₅ is hydroxy or amino, R₆ is C₁₋₄ alkyl or --COR₈, R₉ is hydrogen; C₁₋₄ alkyl; C₅₋₆ cycloalkyl; phenyl; phenyl substituted by 1 to 3 substituents selected from C₁₋₄ alkyl, C₁₋₄ -alkoxy, halo, --COOH and --SO₃ H; phenyl-(C₁₋₄ alkyl); phenyl(C₁₋₄ alkyl) the phenyl ring of which is substituted by 1 to 3 substituents selected from C₁₋₄ alkyl, C₁₋₄ alkoxy, halo, --COOH and --SO₃ H; --COR₈ ; --(CH₂)_(n) --SO₃ H; --(CH₂)_(n) --OSO₃ H or --(CH₂)_(n) --COR₈, wherein n is 1, 2, 3 or 4, R₁₀ is hydrogen; cyano; --SO₃ H; --COR₈ ; C₁₋₄ alkyl; C₁₋₄ alkyl monosubstituted by hydroxy, halo, cyano, C₁₋₄ alkoxy, --SO₃ H, --OSO₃ H, amino or ##STR49## wherein R₁₁ is hydrogen, C₁₋₄ alkyl or C₂₋₄ hydroxyalkyl, and An⊖ is a non-chromophoric anion, andthe ** denotes the carbon atoms to which the --N═N-- radical is attached, a is 1, 2 or 3, and b is 0, 1 or 2, with the proviso that the sum of a and b is a maximum of 3,wherein each R₁ is independently hydrogen, C₁₋₄ alkyl or C₁₋₄ alkyl monosubstituted by hydroxy, halo, --SO₃ H, --OSO₃ H or --COOH, each R₇ is independently hydrogen, halo, C₁₋₄ alkyl, C₁₋₄ alkoxy, --COOH or --SO₃ H, each R₈ is independently hydroxy, C₁₋₄ alkoxy or amino, and each halo is independently fluoro, chloro or bromo.
 2. A compound according to claim 1,or a water-soluble salt thereof each cation of which is independently a non-chromophoric cation, or a mixture of such compounds or water-soluble salts.
 3. A compound according to claim 2,or a water-soluble salt thereof each cation of which is independently a non-chromophoric cation, or a mixture of such compounds or water-soluble salts,wherein Me is Cu or Ni.
 4. A compound according to claim 2,or a water-soluble salt thereof each cation of which is independently a non-chromophoric cation, or a mixture of such compounds or water-soluble salts,wherein each R₁ is independently hydrogen or methyl.
 5. A compound according to claim 2,or a water-soluble salt thereof each cation of which is independently a non-chromophoric cation, or a mixture of such compounds or water-soluble salts,wherein each R₂ and R₃ is independently hydrogen, methyl or ethyl.
 6. A compound according to claim 2,or a water-soluble salt thereof each cation of which is independently a non-chromophoric cation, or a mixture of such compounds or water-soluble salts, wherein Q₄ is linear or branched C₂₋₄ alkylene, linear or branched C₃₋₄ alkylene monosubstituted by hydroxy, ##STR50## wherein W_(c) is linear or branched C₁₋₂ alkylene,m is 0 or 1, and the * denotes the carbon atom attached to the nitrogen atom of the pyridone ring, --Q₄ --NR₁ -- is ##STR51## wherein W_(d) is linear or branched C₂₋₃ alkylene andthe * denotes the carbon atom attached to the nitrogen atom of the pyridine ring, R₄ is hydrogen, methyl, ethoxy, --COOH or --SO₃ H, and R₆ is methyl, --COOH or --CONH₂, R₉ is hydrogen, methyl, ethyl, phenyl, --COR_(8a), --CH₂ SO₃ H or --CH₂ OSO₃ H, and R₁₀ is hydrogen, cyano, --SO₃ H, --COR_(8a) or --CH₂ SO₃ H,wherein each R_(8a) is independently hydroxy or amino.
 7. A compound according to claim 2 having the formula ##STR52## or a water-soluble salt thereof each cation of which is independently a non-chromophoric cation,or a mixture of such compounds or water-soluble salts,wherein Me₁ is Cu or Ni, Pc is the phthalocyanine ring, R_(1b) is hydrogen, methyl, ethyl or 2-hydroxyethyl, each R_(2a) and R_(3a) is independently hydrogen or C₁₋₄ alkyl, or --NR_(2a) R_(3a) is pyrrolidino, piperidino, morpholino or piperazino, R_(4b) is hydrogen, --COOH or --SO₃ H, Y_(b) is ##STR53## wherein Q_(3b) is ##STR54## wherein R_(7a) is hydrogen, chloro, methyl, methoxy, --COOH or --SO₃ H,Q_(4a) is linear or branched C₂₋₄ alkylene, linear or branched C₃₋₄ alkylene monosubstituted by hydroxy, ##STR55## wherein W_(c) is linear or branched C₁₋₂ alkylene, the * denotes the carbon atom attached to the nitrogen atom of the pyridone ring, and m is 0 or 1, or ##STR56## wherein W_(d) is linear or branched C₂₋₃ alkylene and the * denotes the carbon atom attached to the nitrogen atom of the pyridone ring, R_(6a) is methyl, --COOH or --CONH₂, R_(9b) is methyl or ethyl, R_(10b) is hydrogen or --CONH₂, and the ** denotes the carbon atom to which the --N═N-- radical is attached, a1 is 2 or 3, and b1 is 0 or 1, with the proviso that the sum of a1 and b1 is a maximum of
 3. 8. A compound according to claim 7,or a water-soluble salt thereof each cation of which is independently a non-chromophoric cation, or a mixture of such compounds or water-soluble salts,wherein b1 is
 0. 9. A compound of the formula ##STR57## or a salt thereof, or a mixture of such compounds or salts,wherein Me is Cu, Ni, Co, Fe or Al, Pc is the phthalocyanine ring, Q₁ is linear or branched C₂₋₆ alkylene; linear or branched C₃₋₆ alkylene monosubstituted by hydroxy; linear or branched C₂₋₆ alkylene interrupted by one radical selected from --O-- and --NR₁ --; ##STR58## wherein is hydrogen, halo, hydroxy, C₁₋₄ alkyl, C₁₋₄ alkoxy, --COOH or --SO₃ H,W_(a) is linear or branched C₁₋₄ alkylene, and the *** denotes the carbon atom attached to the --SO₂ NR₁ -- radical, or--NR₁ --Q₁ --NR₁ -- is ##STR59## wherein W_(b) is linear or branched C₂₋₄ alkylene, an the *** denotes the nitrogen atom attached to the --SO₂ -- radical, R is C₁₋₆ alkyl, and R₃ is hydrogen or C₁₋₆ alkyl, or --NRR₃ is a pyrrolidine, piperidine, piperazine or morpholine ring, c is 1 or 2, and d is 1 or 2, with the proviso that the sum of c and d is a maximum of 3,wherein each R₁ is independently hydrogen, C₁₋₄ alkyl or C₁₋₄ alkyl monosubstituted by hydroxy, halo, --SO₃ H, --OSO₃ H or --COOH, and each halo is independently fluoro, chloro or bromo.
 10. A compound according to claim 9,or a water-soluble salt thereof each cation of which is independently a non-chromophoric cation, or a mixture of such compounds or water-soluble salts.
 11. A compound according to claim 10,or a water-soluble salt thereof each cation of which is independently a non-chromophoric cation, or a mixture of such compounds or water-soluble salts,wherein Me is Cu or Ni.
 12. A compound according to claim 10,or a water-soluble salt thereof each cation of which is independently a non-chromophoric cation, or a mixture of such compounds or water-soluble salts,wherein each R₁ is independently hydrogen or methyl.
 13. A compound according to claim 10,or a water-soluble salt thereof each cation of which is independently a non-chromophoric cation, or a mixture of such compounds or water-soluble salts,wherein R is methyl or ethyl, and R₃ is hydrogen, methyl or ethyl.
 14. A compound according to claim 10,or a water-soluble salt thereof each cation of which is independently a non-chromophoric cation, or a mixture of such compounds or water-soluble salts,wherein Q₁ is linear or branched C₂₋₃ alkylene, linear or branched C₃₋₄ alkylene monosubstituted by hydroxy, --W_(d) --O--W_(d) --, --W_(d) --NR_(1b) --W_(d) --, ##STR60## wherein R_(1b) is hydrogen, methyl, ethyl or 2-hydroxyethyl,R_(4a) is hydrogen, methyl, methoxy, --COOH or --SO₃ H, W_(e) is linear or branched C₁₋₃ alkylene, and the *** denotes the carbon atom attached to the --SO₂ NR₁ -- radical, or --NR₁ --Q₁ --NR₁ -- ##STR61## wherein the *** denotes the nitrogen atom attached to the --SO₂ -- radical, wherein each W_(d) is independently linear or branched C₂₋₃ alkylene.
 15. A compound according to claim 10 having the formula ##STR62## or a water-soluble salt thereof each cation of which is independently a non-chromophoric cation,or a mixture of such compounds or water-soluble salts,wherein Me₁ is Cu or Ni, Pc is the phthalocyanine ring, Q_(1b) is linear or branched C₂₋₃ alkylene, linear or branched C₃₋₄ alkylene monosubstituted by hydroxy, ##STR63## wherein R_(4b) is hydrogen, --COOH or --SO₃ H,W_(e) is linear or branched C₁₋₃ alkylene, and the *** denotes the carbon atom attached to the --SO₂ NH-- radical, or --NH--Q_(1b) --NR_(1b) -- is ##STR64## R_(a) is C₁₋₄ alkyl, R_(3a) is hydrogen or C₁₋₄ alkyl, or --NR_(a) R_(3a) is pyrrolidino, piperidino, morpholino or piperazino, R_(1b) is hydrogen, methyl, ethyl or 2-hydroxyethyl, c is 1 or 2, and d is 1 or 2, with the proviso that the sum of c and d is a maximum of
 3. 16. A compound according to claim 15,or a water-soluble salt thereof each cation of which is independently a non-chromophoric cation, or a mixture of such compounds or water-soluble salts,wherein d is
 1. 17. A compound according to claim 15,or a water-soluble salt thereof each cation of which is independently a non-chromophoric cation, or a mixture of such compounds or water-soluble salts,wherein R_(a) is methyl or ethyl, and R_(3a) is hydrogen, methyl or ethyl.
 18. A compound according to claim 15,or a water-soluble salt thereof each cation of which is independently a non-chromophoric cation, or a mixture of such compounds or water-soluble salts,wherein R_(1b) is hydrogen or methyl.
 19. A compound according to claim 15,or a water-soluble salt thereof each cation of which is independently a non-chromophoric cation, or a mixture of such compounds or water-soluble salts,wherein Q_(1b) is linear or branched C₂₋₃ alkylene, linear or branched C₃₋₄ alkylene monosubstituted by hydroxy or ##STR65## --NH--Q_(1b) --NR_(1b) -- is ##STR66##
 20. A compound according to claim 19,or a water-soluble salt thereof each cation of which is independently a non-chromophoric cation, or a mixture of such compounds or water-soluble salts,wherein Q_(1b) is linear or branched C₂₋₃ alkylene or linear or branched C₃₋₄ alkylene monosubstituted by hydroxy.
 21. A compound according to claim 20,or a water-soluble salt thereof each cation of which is independently a non-chromophoric cation, or a mixture of such compounds or water-soluble salts,wherein Me₁ is copper. 